RuCl2(CO)(PiPr3)2 | 160731-01-1

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: RuCl2(CO)(PiPr3)2
• 英文别名: carbon monoxide;ruthenium(2+);tri(propan-2-yl)phosphane;dichloride
• CAS: 160731-01-1
• 化学式: C₁₉H₄₂Cl₂OP₂Ru
• 分子量: 520.465
• InChiKey: LEDJLBBWZOURAT-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.73
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  二硫化碳 、 RuCl2(CO)(PiPr3)2 以 氯仿 为溶剂， 以86%的产率得到Carbon monoxide;dichlororuthenium;tri(propan-2-yl)phosphane;tri(propan-2-yl)phosphaniumylmethanedithioate
  参考文献：
  名称：

  Werner, Helmut; Tena, Miguel Angel; Mahr, Norbert, Chemische Berichte, 1995, vol. 128, # 1, p. 41 - 48

  摘要：

  DOI：
• 作为产物：
  描述：

  carbonylchlorohydridobis(triisopropylphosphine)ruthenium(II) 、 氯仿 以 氯仿 为溶剂， 以0%的产率得到RuCl2(CO)(PiPr3)2
  参考文献：
  名称：

  Reactivity of RuCl₂(CO)(P^tBu₂Me)₂ toward H₂ and Brønsted Acids:  Aggregation Triggered by Protonation and Phosphine Loss

  摘要：

  Reaction of H-2 with RuCl2(CO)L(2) (L = P(t)Bu(2)Me) in benzene forms RuHCl(CO)L(2) and HCl. The latter reacts with RuCl2(CO)L(2) to give [LH][Ru2Cl5(CO)(2)L(2)] and [LH]Cl. The Ru2Cl5(CO)(2)L(2)(-) ion is detected (NMR) as several isomers, and is shown by X-ray diffraction to have a face-shared bioctahedral structure: LCl(OC)Ru(mu-Cl)(3)Ru(CO)ClL(-). The loss of phosphine from Ru(II) is triggered by electrophilic attack, but not directly on P or on the Ru-P bond. It is shown (low-temperature NMR studies) that HCl reacts with RuHCl(CO)L(2) to give initially RuCl2(H-2)(CO)L(2), in which H-2 is trans to Cl. From this study, and also direct observation of the reaction of HCl with RuCl2(CO)L(2) to produce Ru2Cl5(CO)(2)L(2)(-), the Bronsted basicity of chloride in RuCl2(CO)L(2) is established. This accounts for its reaction with PhC(2)H and NEt(3) to give Ru(C(2)Ph)Cl(CO)L(2). Crystallographic data (-173 degrees C) for [P(t)Bu(2)MeH][Ru2Cl5(CO)(2)(P(t)Bu(2)Me)(2)]: a = 16.418(2)Angstrom, b = 12.578(2)Angstrom, c = 20.044(3)Angstrom, beta = 103.38(1)degrees with Z = 4 in space group P2(1)/a.

  DOI：

  10.1021/ic9605837
• 作为试剂：
  描述：

  二甲基苯基硅烷 、 苯乙炔 在 RuCl2(CO)(PiPr3)2 作用下， 反应 2.0h， 生成 β-(Z)-2-dimethylphenylsilylstyrene
  参考文献：
  名称：

  的（立体控制合成ë） -和（Ž） -聚（p -phenylenevinylene）s可通过钌催化的氢化硅烷化p -diethynylbenzene

  摘要：

  已经研究了具有（E）-和（Z）-亚乙烯基单元的聚（亚苯基亚乙烯基）s（PPV）的立体控制合成。的钌配合物催化的氢化硅烷p与HSiMe -diethynylbenzene 2的Ar（氩= 2-噻吩基（TH），3,5-（CF 3）2 C ^ 6 ħ 3）容易地在CH前进2氯2在室温下，得到（E，E）-或（Z，Z）-双（2-甲硅烷基乙烯基）苯（3a，3b），产率为89-40％。3a和3b的几何显然取决于所用钌催化剂。因此，RuHCl（CO）（PPh 3）3以超过99％的选择性形成（E，E）异构体，而RuCl 2（CO）（PPr i 3）2则提供（Z，Z）-3a和3b，其92和几何纯度分别为91％。3a和3b的（E，E）-和（Z，Z）-异构体在钯催化剂（[PdCl（η3-烯丙基）2，Pd（dba）2）和四丁基氟化铵水合物，以高收率得到富（E）和富（Z）的PPV。

  DOI：

  10.1016/s0022-328x(03)00266-3

文献信息

• Charge Delocalization in a Heterobimetallic Ferrocene−(Vinyl)Ru(CO)Cl(P^<i>i</i>Pr₃)₂ System†Dedicated to Prof. Dr. Helmut Werner on the occasion of his 75th birthday
  作者：Konrad Kowalski、Michael Linseis、Rainer F. Winter、Manfred Zabel、Stanislav Záliš、Harald Kelm、Hans-Jörg Krüger、Biprajit Sarkar、Wolfgang Kaim

  DOI：10.1021/om9002945

  日期：2009.7.27

  spectrum of 1•+, and the results of quantum chemical calculations indicate that in solution the positive charge partly resides on the vinyl ruthenium moiety. Comparison of IR shifts in the solid state and in solution and the quadrupole splitting in the Moessbauer spectrum of powdered 1•+ point to a larger extent of charge localization on the ferrocenyl site in solid samples. This is probably due to CH···F

  的Ru（CH═CHFc）氯（CO）（P我镨3）2（FC =二茂铁，（η 5 -C 5 H ^ 4）的Fe（η 5 -C 5 H ^ 5）），1，已编制hydroruthenation乙炔基二茂铁的组成，并通过NMR，IR，ESI-MS和Moessbauer光谱以及X射线晶体学进行表征。配合物1具有二茂铁和（乙烯基）钌的氧化还原位点，并经历了两个连续的可逆氧化。结晶的纯样品，monooxidized 1 •+已制备由化学氧化1与二茂铁离子。结构比较图1显示了Fe-C和Fe-Cp中心的增加。键的长度和Cp甲板的环倾斜（如二茂铁离子一样），但在氧化时，Ru-C（CO）和Ru-P键的长度也明显增加，而Ru-C（乙烯基）键的长度却明显缩短。这支持了1 •+中两个氧化还原位点上电荷离域的一般思想。电荷敏感的IR标记的带移（Ru的ν（CO），Fc的ν（CH，Cp）），ESR光谱中1 •+的相当小的g各向
• 14-Electron Four-Coordinate Ru(II) Carbyl Complexes and Their Five-Coordinate Precursors:  Synthesis, Double Agostic Interactions, and Reactivity
  作者：Dejian Huang、William E. Streib、John C. Bollinger、Kenneth G. Caulton、Rainer F. Winter、Thomas Scheiring

  DOI：10.1021/ja990621w

  日期：1999.9.1

  five-coordinate Ru(II) complexes RuHCl(CO)(PiPr3)2, 1, RuCl2(CO)(PiPr3)2, 2, and Ru(Ph)Cl(CO)(PtBu2Me)2, 12, are reported. All three of these complexes have square-based pyramid geometry with the strongest σ-donor ligand trans to the vacant site. These 16-electron complexes do not show bona fide agostic interactions. This is attributed to the strong trans influence ligand (H, CO, and Ph) and π-donation

  五配位 Ru(II) 配合物 RuHCl(CO)(PiPr3)2, 1, RuCl2(CO)(PiPr3)2, 2 和 Ru(Ph)Cl(CO)(PtBu2Me)2, 12 的结构是报道。所有这三种复合物都具有基于正方形的金字塔几何形状，其中最强的 σ-供体配体转移到空位。这些 16 电子复合物没有表现出真正的激动相互作用。这归因于强反式影响配体（H、CO 和 Ph）和 Cl 的 π 供体，这进一步得到以下事实的支持：12 的 Cl-去除产物中存在两种激动相互作用，即四配位 [RuPh(CO)L2]BAr'4 (L = PtBu2Me, Ar' = 3,5-C6H3(CF3)2), 16. 16 和 12 的结构比较表明去除 Cl- 不会改变剩余的配体排列，但为激动相互作用创造了两个低洼的 LUMO，IR 光谱证明它们在溶液中持续存在。16 与 E-H (E = B, C(sp)) 键的反应裂解
• Ruthenium-catalyzed hydrosilylation of terminal alkynes: stereodivergent synthesis of (E)- and (Z)-alkenylsilanes
  作者：Hiroyuki Katayama、Ken Taniguchi、Masayuki Kobayashi、Takashi Sagawa、Tatsuya Minami、Fumiyuki Ozawa

  DOI：10.1016/s0022-328x(01)01319-5

  日期：2002.2

  Stereodivergent hydrosilylation of terminal alkynes (RCequivalent toCH; R = Ph, p-tolyl, Cy, n-hexyl) with hydrosilanes (HSiMe2Ar; Arequivalent toPh, 3.5-(CF3)(2)C6H3, 4-CFC3H4, 4-MeOC6H4) has been examined using ruthenium catalysts. (E)-selective reactions giving (E)-RCH=CHSiMe2Ar proceed in over 99% selectivity in the presence of a catalytic amount of RuHCl(CO)(PPh3)(3). On the other hand, (Z)-selective reactions are successfully conducted in 91-99% selectivity by using Ru(SiMe2Ph)Cl(CO)(PPr'(3))(2) as the catalyst. All reactions readily proceed at room temperature in high yields. (E)- and (Z)-styrylsilanes having a SiMe2[C6H3-3,5-(CF3)(2)] group serve as good cross-coupling reagents with p-iodotoluene in the presence of tetrabutylammonium. fluoride and [Pd(eta(3)-al-lyl)Cl](2) catalyst. (C) 2002 Elsevier Science B.V. All rights reserved.
• Reactivity of RuCl₂(CO)(P<i>^t</i>Bu₂Me)₂ toward H₂ and Brønsted Acids:  Aggregation Triggered by Protonation and Phosphine Loss
  作者：Dejian Huang、Kirsten Folting、Kenneth G. Caulton

  DOI：10.1021/ic9605837

  日期：1996.1.1

  Reaction of H-2 with RuCl2(CO)L(2) (L = P(t)Bu(2)Me) in benzene forms RuHCl(CO)L(2) and HCl. The latter reacts with RuCl2(CO)L(2) to give [LH][Ru2Cl5(CO)(2)L(2)] and [LH]Cl. The Ru2Cl5(CO)(2)L(2)(-) ion is detected (NMR) as several isomers, and is shown by X-ray diffraction to have a face-shared bioctahedral structure: LCl(OC)Ru(mu-Cl)(3)Ru(CO)ClL(-). The loss of phosphine from Ru(II) is triggered by electrophilic attack, but not directly on P or on the Ru-P bond. It is shown (low-temperature NMR studies) that HCl reacts with RuHCl(CO)L(2) to give initially RuCl2(H-2)(CO)L(2), in which H-2 is trans to Cl. From this study, and also direct observation of the reaction of HCl with RuCl2(CO)L(2) to produce Ru2Cl5(CO)(2)L(2)(-), the Bronsted basicity of chloride in RuCl2(CO)L(2) is established. This accounts for its reaction with PhC(2)H and NEt(3) to give Ru(C(2)Ph)Cl(CO)L(2). Crystallographic data (-173 degrees C) for [P(t)Bu(2)MeH][Ru2Cl5(CO)(2)(P(t)Bu(2)Me)(2)]: a = 16.418(2)Angstrom, b = 12.578(2)Angstrom, c = 20.044(3)Angstrom, beta = 103.38(1)degrees with Z = 4 in space group P2(1)/a.
• Werner, Helmut; Tena, Miguel Angel; Mahr, Norbert, Chemische Berichte, 1995, vol. 128, # 1, p. 41 - 48
  作者：Werner, Helmut、Tena, Miguel Angel、Mahr, Norbert、Peters, Karl、Schnering, Hans-Georg von

  DOI：——

  日期：——